Chirality, Carbonyls and Carboxylic Acids

Questions on this unit may include material from UNIT 2 see syllabus
Isomerism
Structural isomerism. Structural isomerism was dealt with in UNIT 2.
All isomers are compounds with the same molecular formula. e.g. C 4 H 10 or C 2 H 6 O.
Structural isomers have atoms arranged in different orders. They have similar bpt's.
e.g.

CH 3 CH 2 CH 2 CH 3 (butane) and CH 3 CH(CH 3 )CH 3 (2-methylpropane)

CH 3 CH 2 OH (ethanol) and CH 3 OCH 3 (methoxymethane)

Stereoisomerism.
Stereoisomers have the same molecular formula and the same structural formula.
The same atoms are arranged in the same order but with different orientations in space.
Geometric, cis-trans, or E-Z isomerism - also dealt with in UNIT 2 - is one form of
stereoisomerism.
Another form is optical isomerism.

Chirality
Chirality leads to optical isomerism. Optical isomerism occurs when two compounds have the
same molecular formula, but are not superimposable on each other.
If a compound contains a carbon atom bonded to four different groups or atoms, it can exist in
two forms which are mirror images of each other.
Example CH 3 CH(OH)CO 2 H

CH 3 CH(OH)CO 2 H

HO
H3C

CO2H

HO2C

OH
CH3

The two isomers affect polarised light by rotating the plane of polarisation of plane polarised
monochromatic light in opposite directions; this is where the term "optical" comes from.
Optical isomers differ only in the extent to which they rotate the plane of polarised monochromatic
light. Optical isomers exist in two forms called enantiomers. The dextrorotatory (+) form rotates
light to the right (clockwise) but the laevorotatory (-) rotates light to the left.
A sample of an optically active substance may contain both optically active isomers.
An equimolar mixture does not rotate light at all as equal and opposite rotations cancel. This
optically inactive mixture is called the racemic mixture or racemate.
The carbon atom with four different groups around it (the chiral centre) is said to be assymetric.
The two mirror image molecules are said to be chiral.

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Carbonyl Compounds
Introduction
Carbonyl compounds contain the C=O group.
When this group occurs at the end of a carbon chain, the compound is an aldehyde (RCHO), the
name ending in al. When group occurs within the carbon chain, the compound is a ketone
(RCOR 1 ), the name ending in one.

H
H C
H
H
H C
H

H
C
H

H
C
H
Pentanal
H
C
H

H
C
H

H
C

C
H

O
H
H
C
C
C
H
H
Pentan-3-one

H
H C
H

O
C
H

O
C

H
C

H
C H
H
H
C H
H

H C H
3-Methylbutan-2-one H

H C H
2-Methylbutanal

H
H C
H

The carbonyl group in polar because of the electronegative oxygen atom.

The geometry around the carbonyl group is planar, with bond angles of about 120o.

Physical Properties
Carbonyl compounds are much more volatile than the corresponding alcohol because, unlike
alcohols, they do not have any hydrogen bonding. They are less volatile than an alkane of similar
formula mass because of the polarity of the molecules.
Compound
Formula
Formula mass
Boiling point /oC
Propane
C3H8
44
-42
Ethanal
CH 3 CHO
44
20
Ethanol
C 2 H 5 OH
46
78
Although carbonyl compounds do not have a hydrogen which is directly connected to the oxygen,
and therefore they have no hydrogen bonding, when placed in water the oxygen in the carbonyl is
able to form a hydrogen bond with the hydrogen in the water molecules. This makes the carbonyl
compounds, especially those with short carbon chains, very soluble in Water.

Chemical Properties
Aldehydes and ketones are both attacked by nucleophiles, and can both be reduced to alcohols.
However, only aldehydes can be readily oxidised, and this is the basis for tests to distinguish
between them.
Aldehydes and ketones are obtained by oxidation of primary and secondary alcohols,
respectively.

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The test for a carbonyl group.

All carbonyl compounds react with 2,4-dinitrophenylhydrazine (Brady's reagent).
When a solution of 2,4-dinitrophenylhydrazine is added to a carbonyl, a reaction takes place at
room temperature producing orange crystals.
This is used as the test for the presence of the carbonyl group.
Ethanal and 2,4-dinitrophenylhydrazine

NO2

NO2
CH3

CH3
C

H2N

NO2

NH

NO2

NH

+ H2O
Propanone and 2,4-dinitrophenylhydrazine

NO2

NO2
CH3

CH3
C

H2N

NO2

NH

NO2

NH

CH3

CH3

+ H2O
Propanal and 2,4-dinitrophenylhydrazine

NO2

NO2
C2H5

C2H5
C

H2N

NH

NO2

NH

+ H2O

Oxidation
Aldehydes are reducing compounds and can react with some oxidising agents.
Since ketone cannot be oxidised, they do not take part in oxidation reactions.
This is used as a test for distinguishing between aldehydes and ketones.
Aldehydes will react when heated with ammoniacal silver nitrate solution (Tollen's reagent).
This is a reaction in which the aldehyde is oxidised, and the silver ions are reduced to silver.
When carried out in a clean test tube it forms a silver mirror.
RCHO(aq) + Ag(NH 3 ) 2 +(aq) + H 2 O RCOOH(aq) + Ag(s) + 2NH 4 +(aq)
Silver mirror

-3

NO2

Aldehydes will also react with other oxidizing agents. These tests are summarized below;
Oxidising agent

Tollens reagent
Fehlings solution
Dichromate solution

Conditions
Heat aldehyde with ammoniacal
silver nitrate
Heat aldehyde with Fehlings
solution
Heat aldehyde with a mixture of
potassium dichromate solution and
sulphuric acid

Result for aldehyde

Silver mirror forms
Turns from a blue solution to
form a red precipitate
Turns from an orange solution
to a green solution

Aldehydes with Fehlings solution (oxidation)

Aldehydes (but not ketones) reduce Cu2+ to Cu+ giving a red brown precipitate of copper (I) oxide
in this test.
Drops of the carbonyl compound are added to equal volumes of Fehling's solutions A and B.
The mixture is warmed in a water bath. (oxidation)
RCHO(aq) + 2Cu2+(aq) + 2H 2 O(l) RCOOH(aq) + 4H+(aq) +Cu 2 O(s)

Reduction
Carbonyl compounds are formed by oxidation of alcohols.
The reverse of this process, reduction, converts carbonyls back into alcohols[*].
This reduction can be carried out by reducing agents such as lithium tetrahydridoaluminate(III)
(lithium aluminium hydride} with dry ether as a solvent or sodium tetrahydridoborate(III) (sodium
borohydride} in water.
Note - In equations showing reduction the reducing agent is written as [H].
e.g.

The reduction of propanal to propan-1-ol.

CH 3 CH 2 CHO + 2[H]

CH 3 CH 2 CH 2 OH

CH 3 CH(OH)CH 3

The reduction of propanone to propan-2-ol. CH 3 COCH 3 + 2[H]

Nucleophilic addition
Carbonyl compounds with the C=O group, can undergo addition reactions.
In this case the attack is by a nucleophile being drawn to the molecule by the partial positive
charge on the carbon. Hydrogen cyanide will add on across the C=O bond.
To carry out this reaction, a mixture of potassium cyanide and ethanoic acid is used to avoid
use of the very poisonous hydrogen cyanide. These reactions take place at room temperature
with the mixture buffered at pH 8.
Ethanal and HCN

O
C
H3C

OH
+ KCN, pH 8
(HCN)
H

-4

CH
H3C

CN

Propanone and HCN

O
C
H3C

OH
+ KCN, pH 8
(HCN)
CH

C
H3C

CN
CH3

Reaction mechanism
In this reaction the initial attack is by the cyanide ion. The cyanide ion is a nucleophile which is
attracted to the partial positive charge on the carbonyl carbon created by the electronegative
oxygen.
The reaction has to be carried out in slightly basic conditions, so the mixture is buffered at pH8.
This is to allow the formation of the cyanide ion from the hydrogen cyanide.
H+ + CN-

HCN

If the pH is lower than 8, the dissociation of the HCN lies too far to the left and so the
concentration of CN- is too low for the first step to take place.

C
N

-.

H+

H3C

H3C
+

NC

H3C

-.

NC

OH

If the pH is higher than 8, the concentration of H+ ions is too low for the second stage of the
mechanism to take place.

Reaction of iodine in alkali

Iodine in alkali reacts with a specific group, CH 3 COR to produce a yellow precipitate of CI 3 H.
RCO 2 is also formed in this reaction.
This is used as a test for the presence of the CH 3 COR group.
(Ethanal, ethanol or any methyl ketone can react in this reaction).
The iodine present in the testing reagent can oxidise alcohols, and so CH 3 CHOHR will initially
form CH 3 COR this will then react to give the yellow crystals. The old name for these crystals of
triiodomethane is iodoform, and this reaction is often referred to as the iodoform reaction.
The test is carried out by adding aqueous sodium hydroxide to iodine solution until the mixture
just turns colourless. The organic material is then added, and the mixture is warmed.
CH 3 COR and CH 3 CHOHR give a positive iodoform reaction (where R can be a carbon chain or
hydrogen).
Which of the following will give a positive iodoform reaction?
CH 3 CH 2 CHO
CH 3 CHOHCH 3

No

CH 3 CH 2 COCH 3
Yes

HCHO

-5

Yes
No

Carboxylic acids
Introduction
Carboxylic acids are compounds containing the carboxyl group, CO 2 H, which consists of the C=O
group and the OH group on the same carbon.
The name carboxyl comes from a combination of the names of these functional groups;
Carbonyl + hydroxyl = Carboxyl

H
H C
H

H
C
H

H
H C
H

C
H

H
C
H

H
H C
H

H
C

C
O

H
C
H

C
H

Butanoic acid

Propanoic acid

H
H C
H

H
C
H

H
C

H
C
H

O
C
O

H C H

H C H

3-Methylbutanoic acid

2-Methylbutanoic acid H

Physical Properties
The Carboxyl carbon contains two oxygen atoms both of which are electronegative leaving the
carbon with a partial positive charge. This allows carboxylic acids to form stronger hydrogen than
alcohols, and they therefore have higher boiling pints than alcohols of similar formula mass.
Compound
Propanol
Ethanoic acid

Formula
CH 3 CH 2 CH 2 OH
CH 3 CO 2 H

RFM
60
60

Boiling point /oC

97
118

The structure of the carboxyl group allows carboxylic acid to form dimers

O
R

C
O

Ethanoic acid has a melting temperature of 17oC, so if the temperature falls below this it freezes,
and the similarity of frozen ethanoic acid to ice has given the pure acid the common name of
glacial ethanoic acid.
The ability of carboxylic acids to form hydrogen bonds means that the lower members of the
homologous series (those with up to 4 carbon atoms) are miscible in all proportions with water.
The longer the carbon chain, the less soluble in water the carboxylic acid becomes.

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Preparation of carboxylic acids

Carboxylic acids can be prepared by
Oxidation of primary alcohols
Oxidation of aldehydes
Hydrolysis of nitriles
Preparation from primary alcohols
When a primary alcohol is heated under reflux with potassium dichromate and sulphuric acid a
carboxylic acid is produced.
RCO 2 H + H 2 O
RCH 2 OH + 2[O]
Preparation from aldehydes
When an aldehyde is heated under reflux with potassium dichromate and sulphuric acid a
carboxylic acid is produced.
RCHO + [O]

RCO 2 H
Preparation from nitriles
Carboxylic acids can be formed by hydrolysis of nitrile (RCN) compounds.
The hydrolysis can be carried out by heating the nitrile with acid or alkali.
Hydrolysis using dilute hydrochloric acid.

RCO 2 H + NH 4 Cl
RCN + 2H 2 O + HCl
Hydrolysis using aqueous sodium hydroxide produces the salt of the carboxylic acid.
RCN + H 2 O + NaOH RCO 2 Na + NH 3
The acid can be obtained from the salt by adding a strong acid.
RCO 2 Na + HCl

RCO 2 H + NaCl

Chemical Properties
Reduction
Carboxylic acids are formed by the oxidation of primary alcohols, and can be converted back to
these compounds using lithium tetrahydridoaluminate(III) (lithium aluminium hydride} as a
reducing agent. The acid is treated with lithium aluminium hydride in ether, followed by the
addition of water.
e.g. Reduction of propanoic acid.

CH 3 CH 2 CO 2 H + 4[H]

Reduction of methanoic acid.

HCO 2 H + 4[H]

CH 3 CH 2 CH 2 OH + H 2 O
CH 3 OH + H 2 O

Reaction with alcohols

Carboxylic acids react with alcohols in the presence of concentrated sulphuric acid to form water
and an ester. The carboxylic acid is mixed with alcohol and concentrated sulphuric acid is added.
The mixture is then warmed.
RCOOH + R*OH

RCOOR* + H 2 O
e.g.
H2O

Propanoic acid + ethanol CH 3 CH 2 CO 2 H + CH 3 CH 2 OH CH 3 CH 2 COOCH 2 CH 3 +

Ethyl propanoate

Esters are named from the alkyl group of the alcohol and the oate from the carboxylic acid.
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The esters formed contain the ester functional group or ester link. This has the structure shown
below.
RCOOH + R*OH
RCOOR* + H 2 O

O
C

R*

Ester group

Esters have characteristic odours, which makes them useful for flavouring. Pear drops and
pineapple flavourings are derived from the appropriate ester. Esters are also useful as solvents.

Reaction with phosphorus pentachloride

The -OH group in the acid will react with halogenating reagents, such as phosphorus
pentachloride in the same way as the OH group in alcohols. These reactions occur at room
temperature.
The organic product of these reactions are acyl chlorides (or acid chlorides). This functional
group has the structure shown below.

O
R

Acyl chloride group

Cl

Ethanoic acid reacts with phosphorus pentachloride to produce ethanoyl chloride.

CH 3 COCl + HCl + POCl 3

CH 3 CO 2 H + PCl 5
Ethanoyl chloride
Propanoic acid reacts with phosphorus pentachloride to produce propanoyl chloride.
CH 3 CH 2 CO 2 H + PCl 5 CH 3 CH 2 COCl + HCl + POCl 3
Propanoyl chloride

Neutralisation reactions
Carboxylic acids react with alkalis, carbonates and hydrogencarbonates to form salts.
Reaction with sodium hydroxide

RCO 2 H + NaOH

Reaction with sodium carbonate.

2RCO 2 H + Na 2 CO 3

RCO 2 -Na+ + H 2 O

2RCO 2 -Na+ + H 2 O + CO 2

Reaction with sodium hydrogencarbonate

RCO 2 H + NaHCO 3 RCO 2 -Na+ + H 2 O + CO 2
Such reactions, using titration with a known concentration of alkali and appropriate indicator, can
be used to determine the quantity of acid present. For example this technique can be used to find
the quantity of citric acid in fruit.

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Derivatives of Carboxylic acids

Organic compounds made from carboxylic acids are called derivatives of carboxylic acids.
This includes acyl chlorides and esters.

Esters
The ester functional group is

O
C

R*

Esters can be hydrolysed by boiling with acid or alkali.

When hydrolysed by acid, the alcohol and the carboxylic acid are reformed.
This is a reversible reaction, so does not go to completion.
R1CO 2 H + R2OH
R1COOR2 + H 2 O
When hydrolysed by an alkali, the alcohol and the salt of the carboxylic acid are formed.
Since the carboxylic acid is not formed, this reaction can go to completion.
Such a reaction is called saponification.
R1COOR2 + NaOH

R1CO 2 -Na+ + R2OH

e.g. Acid hydrolysis of CH 3 CH 2 CO 2 CH 2 CH 3

CH 3 CH 2 CO 2 CH 2 CH 3 + H 2 O

CH 3 CH 2 CO 2 H + CH 3 CH 2 OH

Hydrolysis of CH 3 CH 2 CO 2 CH 2 CH 3 by sodium hydroxide solution

CH 3 CH 2 CO 2 CH 2 CH 3 + NaOH CH 3 CH 2 CO 2 -Na+ + CH 3 CH 2 OH
Acid hydrolysis of (CH 3 ) 3 COCOCH 3
(CH 3 ) 3 COCOCH 3 + H 2 O

CH 3 CO 2 H + (CH 3 ) 3 COH

Hydrolysis of (CH 3 ) 3 COCOCH 3 by sodium hydroxide solution

(CH 3 ) 3 COCOCH 3 + NaOH CH 3 CO 2 -Na+ + (CH 3 ) 3 COH
The reaction of natural esters with sodium hydroxide solution is used to make soap.
An animal fat is an ester formed from propan-1,2,3-triol and carboxylic acids with long chains.
CH 2 OCOC 17 H 35
HCOCOC 17 H 35
CH 2 OCOC 17 H 35

+ 3KOH

CH 2 OH
HCOH
+ 3 C 17 H 35 COO-K+
CH 2 OH

Animal fat

glycerol

stearate salt = SOAP

The products on saponification are propan-1,2,3-triol and the salt of the carboxylic acid.

-9

The structure of the salt of the carboxylic acid is shown below.

+
Na

O
C

The charges on the molecule give the useful properties of soap. The charged section is attracted
to the polar water molecules is hydrophilic. The hydrocarbon section is repelled by the water
molecules is hydrophobic. The soap molecule can be pictured as like a tadpole with
hydrophilic head and hydrophobic tail.

The hydrophilic head is attracted into the water and the

hydrophobic tail is repelled by water so the molecules
arrange themselves as shown here. This breaks down
the surface tension of the water and allows it to wet a
surface.

Water

Polyesters
The reaction of an alcohol and a carboxylic acid to form an ester can be used to form polymers in
which the monomers are joined by an ester link. Such a polymer is called a polyester. This is an
example of a condensation polymer in which monomers join by ejecting a small molecule (water
in the case of a polyester).
nHOCH 2 CH 2 OH + nHO 2 C-C 6 H 4 -CO 2 H
ethane-1,2-diol
benzene-1,4dicarboxylic acid

-(-CH 2 CH 2 -O-CO-C 6 H 4 -CO-O-)- n + nH 2 O

Terylene

Transesterification
The burning of diesel oil from petroleum is not an environmentally sustainable method of
providing energy. An alternative is to use natural oils from plants that are renewable.
Such oils will only partially combust in a normal diesel engine, and will therefore cause clogging of
the engine. Engines can be modified to burn this type of fuel.
An alternative is to convert the triglyceride in the fat or oil to a methyl ester. The methyl ester is
more volatile and can be used in a normal diesel engine. The methyl ester can be formed in a
process called transesterification.
Most biodiesel is produced by base-catalysed transesterification
O
H2C O C
O
HC O C

+ 3CH3OH

H2C O C
O

H2C

OH

HC

OH

H2C

H3C

O
C
Bio Diesel

OH

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Acyl chlorides
The acyl chloride functional group is

O
R

C
Cl

Acid chlorides are highly reactive compounds.

They are readily hydrolysed at room temperature, and will fume in moist air due to this reaction.
Important reactions of acyl chlorides are;
Hydrolysis (reaction with water)
Reaction with alcohols
Reaction with concentrated ammonia
Reaction with amines

Hydrolysis
In hydrolysis the acid chloride is converted to the carboxylic acid and HCl is produced.
Reaction with water
RCOCl + H 2 O RCO 2 H + HCl

Reaction with alcohols

They react with alcohols at room temperature to produce the ester.
RCOCl + R#OH RCOOR# + HCl

Reaction with concentrated ammonia

They react with concentrated ammonia at room temperature to produce acid amides.
RCOCl + NH 3 RCONH 2 + HCl

Reaction with amines

They react with amines at room temperature to produce secondary substituted amides.
An amine is a a carbon chain attached to the NH 2 functional group.
RCOCl + R#NH 2 RCO-NH-R#

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